Lecture 10

20/1/2024
 So Far …
❖ Radius-Ratio
❖ Voids
 Voids in FCC

Voids / Voids /
FCC voids Position
cell atom
¼ way from each vertex of
the cube along body
Tetrahedral 8 2
diagonal <111>
→ ((¼, ¼, ¼))
• Body centre: 1 → (½, ½, ½)
Octahedral • Edge centre: (12/4 = 3) → 4 1
(½, 0, 0)
Size of Voids in FCC
Size of Voids in FCC

NPTEL
 Voids in FCC

Interstitial Sites in Face-Centered Cubic

Let’s find the size of those interstitial sites (R), compared
to the size of an atom (r).

FCC tetrahedral site:

FCC octahedral site:

NPTEL lecture
by Prof. Prasad
msestudent.com
 Voids in FCC

FCC tetrahedral site:

FCC octahedral site:

An FCC crystal can fill about

7% of it’s volume with
interstitial atoms!

NPTEL
Voids in FCC
Voids in FCC

NPTEL
Voids in FCC

NPTEL
Voids in BCC

NPTEL
 Voids in BCC

BCC tetrahedral site:  0.29 r

BCC octahedral site:

https://msestudent.com/interstitial-sites-size-types-applications-and-
calculations/
Voids in BCC

NPTEL
Voids in HCP

NPTEL
Voids in HCP

NPTEL
Voids in HCP

NPTEL
Voids in HCP

NPTEL
Voids in HCP

NPTEL
Voids in SC

NPTEL
Voids in SC

NPTEL
Fe/C

NPTEL
Voids Size: Summary

NPTEL
Lecture 11
23/1/2024
So Far …
❖ Void size
 Ceramic Crystals: Real Systems

❑ The atomic bonding is predominantly ionic → crystals

made of electrically charged ions instead of atoms

❑ Two characteristics:
❑ Charge neutrality
❑ Cation/anion size

https://crystalviz.symotter.org/

VESTA
Ceramic Crystals: Real Systems
❑ Cation/anion size
❑ most common CN 4, 6, and 8
❑ Based on geometrical
considerations and assuming
“hard sphere” ions
❑ Covalency can break the rule
(no crystal 100% ionic)
❑ The size of an ion will depend on
several factors: coordination
number
 Ceramic Structures of MX: CsCl

MX: M is a metallic element and X is a nonmetallic element.

• Not a body-centered structure

• The two-atom basis (0,0,0) and
(1/2,1/2,1/2)
• Simple cubic Bravais lattice
• The coordination number is 8 for
both ion types
• Not closed packed
 Ceramic Structures: CsCl

Two interpenetrating cubes,

one of Cs+ and one of Cl-
 Ceramic Structures: CsCl

These are halides of large monovalent elements and a

variety of intermetallic compounds
Ceramic Structures: Packing Fraction
Ceramic Structures: NaCl
Rock Salt Structure

➢ The coordination number for

both cations and anions is 6
➢ An FCC arrangement of
anions with one cation
situated at the cube center
and one at the center of
each of the 12 cube edges
➢ FCC Bravais lattice with two
ions (1 Na+ and 1 Cl-)
associated with each lattice
 Ceramic Structures: NaCl

The (NaCl6) or (ClNa6) octahedra share common edges

Ceramic Structures: NaCl
 Ceramic Structures: NaCl

ccp/fcc anions with octahedral sites fully occupied by

cations and tetrahedral sites empty
Ceramic Structures: NaCl

➢ The intertwining of two FCC structures,

one of sodium ions and one of chlorine
ions
➢ Packing fraction = 74%
Ceramic Structures: NaCl

➢ The exposed plane of anions

(green spheres inside the
triangle) is a [111]-type plane;
the cations (red spheres)
occupy the interstitial
octahedral positions.
Ceramic Structures: Zinc Blende (ZnS)

r+/r- = 0.39

➢ Tetrahedral ion
arrangement
➢ All corner and face
positions of the cubic cell
are occupied by S atoms,
➢ Zn atoms fill interior
tetrahedral voids
➢ It has ccp/fcc anions
Ceramic Structures: Zinc Blende (ZnS)

Zn2+
S2-
Ceramic Structures: Zinc Blende (ZnS)

➢ The faces of the tetrahedra

are parallel to the cp anion
layers i.e. {111} planes
➢ ZnS → cp layers of sulfide
anions with zinc cations in
tetrahedral sites
 Ceramic Structures: Zinc Blende (ZnS)

➢ Oxides do not usually have the zinc blende structure

➢ The chalcogenides (S, Se, Te) are more commonly found in
this crystal structure
 AmXp-Type Crystal Structures

AmXp → m≠p; generally, more complicated structures

AX2 → a common crystal structure is found in fluorite (CaF2)

➢ The ionic radii ratio rC/rA for

CaF2 is about 0.8 → CN = 8
for Ca
➢ CN = 4 for F
➢ Calcium ions are positioned
at the centers of cubes, with
fluorine ions at the corners
Lecture 12
24/1/2024
 So Far …
❖ MX ceramic structures
 AmXp-Type Crystal Structures

Filled
cube
with Ca

➢ One conventional unit cell consists of eight cubes

➢ Primitive cubic array of anions in which the eight-coordinate
sites at the cube body centers are alternately empty and
occupied by a cation
➢ Crystal structure would be similar to CsCl; except that only
half the center cube positions are occupied by Ca2+ ions.
 AmXp-Type Crystal Structures
A2X → antifluorite (Na2O)
▪ Anion : 8 coordinated
▪ Cation: 4 coordinated

General rule for CN in AmXp: The coordination

numbers of A and X must be in the ratio of p:m
Crystal Structures with ccp/fcc anions
 Ceramic Crystal Structures
Start with an
FCC lattice

➢ 1,2,3,4 → All are octahedral void

➢ 5-12 → All are tetrahedral void

All octahedral voids are filled → NaCl structure

Half of the tetrahedral voids are filled → ZnS structure
All the tetrahedral voids are filled → Antifluorite (Na2O) structure
 Na2O Crystal Structure

New origin

▪ Displace the unit cell along a body diagonal by one-quarter

of the length of the diagonal
▪ Cation at ¼ ¼ ¼ can be considered as new origin
 Diamond-Type Crystal Structures

How many
atoms?
Lattice?
Basis ?

➢ The diamond structure is obtained when the two elements in

zinc blende are identical, as in diamond
➢ It may therefore be described as a ccp array of carbon
atoms, with one set of tetrahedral sites occupied also by
carbon atoms
➢ Most Group IV elements crystallize with the diamond structure
Wurtzite (ZnS) Crystal Structure:
Voids in HCP
 Wurtzite (ZnS) Crystal Structure

Projection down c-axis

HCP arrangement of anions

 Wurtzite (ZnS) Crystal Structure

HCP
arrangement of
anions
 Wurtzite (ZnS) Crystal Structure

HCP
arrangement of
anions
 Wurtzite (ZnS) Crystal Structure

Projection down c-axis

➢ HCP arrangement of anions

➢ The unit cell contains two anions, one at the origin and one
inside the cell: (0 0 0) and (1/3, 2/3, 1/2)
➢ Close packed layers occur in the basal plane, at c = 0
(blue circles), and at c = 1/2 (pink circles)
➢ ..ABABAB… stacking
Wurtzite (ZnS) Crystal Structure
Wurtzite
structure:
Base with S and
tetrahedral
void with Zn

Zn is in T+ sites
 Zinc Blende and Wurtzite (ZnS) Crystal Structure

Zinc Blende Wurtzite

structure structure

▪ Very similar and both can be regarded as networks of

tetrahedra.
▪ In zinc blende → ABC stacking
▪ In wurtzite → AB sequence
 NiAs Crystal Structure

➢ The octahedral site is coordinated to three anions at c = 0

and three anions at c = ½
➢ Octahedral site = 2/3,1/3, ¼

NiAs structure:
Base with As and Octahedral void with Ni
 AmBnXp-Type Crystal Structures

A ➢ Ceramic compounds with more than

one type of cation
➢ Two types of cations (represented by
B A and B) in perovskite crystal structure
➢ Ti-O distance = a/2
➢ Ba-O distance = a/2
➢ CN of Ti, Ba, O are 6, 12, 2
➢ A variety of distorted, non-cubic
structures exist.
A unit cell for the
➢ Lower-symmetry structures often form
perovskite
on cooling the high-temperature
cubic structure and the framework of
octahedra may be slightly twisted or
distorted
 Ceramic Density Computations
Theoretical density of a
crystalline ceramic
material from unit cell data

n = the number of formula units1 within the unit cell

AC = sum of the atomic weights of all cations in the formula unit
AA = sum of the atomic weights of all anions in the formula unit
 Ceramic Density Computations
On the basis of crystal structure, compute the theoretical
density for sodium chloride.

n = 4; both sodium and chloride ions form FCC lattices

VC = a3; a is the unit cell edge length

 Silica (SiO2)
➢ Widely available in raw materials in the earth’s crust
➢ Its structure is not simple; there is not a single structure to
describe it
➢ Each atom of silicon is bonded to four oxygen atoms,
which are situated at the corners of the tetrahedron
➢ Often not considered to be ionic as there is a significant
covalent character to the interatomic Si–O bonds

silicon–oxygen
(SiO44-) tetrahedron
Silica (SiO2)

➢ Cristobalite (SiO2): built on FCC

Bravais lattice with six ions (2Si4+ and
4O2-) associated with each lattice
point